19617-44-8Relevant articles and documents
Reaction of Ethyl Chlorosodiocarbamate with Organic Azides
Gibson, Harry H.,Macha, Matthew R.,Farrow, Sherry J.,Ketchersid, Terry L.
, p. 2062 - 2065 (1983)
Ethyl chlorosodiocarbamate (3) is reactive as a nucleophile toward ethyl azidoformate (4) and tosyl azide but not toward alkyl or aryl azides.Diethyl iminodiformate (5), nitrogen gas, and sodium chloride are the principal products from the reaction of 3 with 4.Mechanistic studies support a reaction scheme involving attack of 3 at the carbonyl group of azide 4, instead of attack at the terminal azido nitrogen.The results of this study are correlated with hard and soft acid and base theory.
Unexpectedly Stable (Chlorocarbonyl)(N-ethoxycarbonylcarbamoyl)disulfane, and Related Compounds That Model the Zumach-Weiss-Kühle (ZWK) Reaction for Synthesis of 1,2,4-Dithiazolidine-3,5-diones
Barany, George,Britton, Doyle,Chen, Lin,Hammer, Robert P.,Henley, Matthew J.,Schrader, Alex M.,Young, Victor G.
, p. 11313 - 11321 (2015/12/01)
The Zumach-Weiss-Kühle (ZWK) reaction provides 1,2,4-dithiazolidine-3,5-diones [dithiasuccinoyl (Dts)-amines] by the rapid reaction of O-ethyl thiocarbamates plus (chlorocarbonyl)sulfenyl chloride, with ethyl chloride and hydrogen chloride being formed as coproducts, and carbamoyl chlorides or isocyanates generated as yield-diminishing byproducts. However, when the ZWK reaction is applied with (N-ethoxythiocarbonyl)urethane as the starting material, heterocyclization to the putative "Dts-urethane"? does not occur. Instead, the reaction directly provides (chlorocarbonyl)(N-ethoxycarbonylcarbamoyl)disulfane, a reasonably stable crystalline compound; modified conditions stop at the (chlorocarbonyl)[1-ethoxy-(N-ethoxycarbonyl)formimidoyl]disulfane intermediate. The title (chlorocarbonyl)(carbamoyl)disulfane cannot be converted to the elusive Dts derivative, but rather gives (N-ethoxycarbonyl)carbamoyl chloride upon thermolysis, or (N-ethoxycarbonyl)isocyanate upon treatment with tertiary amines. Additional transformations of these compounds have been discovered, providing entries to both known and novel species. X-ray crystallographic structures are reported for the title (chlorocarbonyl)(carbamoyl)disulfane; for (methoxycarbonyl)(N-ethoxycarbonylcarbamoyl)disulfane, which is the corresponding adduct after quenching in methanol; for [1-ethoxy-(N-ethoxycarbonyl)formimidoyl](N′-methyl-N′-phenylcarbamoyl)disulfane, which is obtained by trapping the title intermediate with N-methylaniline; and for (N-ethoxycarbonylcarbamoyl)(N′-methyl-N′-phenylcarbamoyl)disulfane, which is a short-lived intermediate in the reaction of the title (chlorocarbonyl)(carbamoyl)disulfane with excess N-methylaniline. The new chemistry and structural information reported herein is expected to contribute to accurate modeling of the ZWK reaction trajectory.
Synthesis of 1-Oxo-1H-pyrazolotriazol-4-ium-3-olates. - A Ring-Chain Tautomerism in the Series of Bicyclic Dipolar Heterocycles
Boettcher, Andreas,Debaerdemaeker, Tony,Radziszewski, Juliusz G.,Friedrichsen, Willy
, p. 895 - 908 (2007/10/02)
1-(Trimethylsilyl)pyrazole (12) reacts with chlorocarbonyl isocyanate to give a compound, which - dependent on the state of aggregation - may exist both as a bicyclic dipolar heterocycle (7) and as monocyclic 1-pyrazolyl carbonyl isocyanate (8).Methyl-substituted derivatives (19a, b) show a similar behaviour.MNDO calculations for the parent systems (7, 8) are in accord with these experimental observations.The structure of 5,6,7-trimethyl-1-oxo-1H-pyrazolotriazol-4-ium-3-olate (19b) has been clarified by X-ray analysis.
The photochemical addition of N-haloamides to olefins: a comparison of cyclic and acyclic N-halo-N-alkylamides and N-halo-N-acylamides (N-haloimides)
Lessard, Jean,Couture, Yvon,Mondon, Martine,Touchard, Daniel
, p. 105 - 112 (2007/10/02)
Upon photochemical decomposition in the presence of cyclohexene and 1-octene, an N-halo-N-acylamide (N-haloimide) leads to better yields of addition than its N-halo-N-alkyl analogue, and cyclic N-halo-N-alkyl and N-halo-N-acylamides add more efficiently than their acyclic analogues.The yields of addition were higher with N-chlorosuccinimide which has been added also to 1-methylcyclohexene than with N-bromosuccinimide which did not add to 1-methylcyclohexene.
